Comparison of bitumens from oil sands with different recovery profiles

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Comparison of bitumens from oil sands with different recovery profiles

Woods, J. R.; Kung, J.; Kingston, D.; McCracken, T.; Kotlyar, L. S.; Sparks, B. D.; Mercier, P. H. J.; Ng, S.; Moran, K.

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COMPARISON OF BITUMENS FROM OIL SANDS WITH DIFFERENT RECOVERY PROFILES

RECOVERY PROFILES

J.R. Woods1_{, J. Kung}1_{, D. Kingston}1_{, T. McCracken}1_{, L.S. Kotlyar}1_{, B.D. Sparks}2_,

P.H.J. Mercier1_{, S. Ng}3 _{and K. Moran}3

1. National Research Council of Canada 2. V. Bede Technical Associates

3. Syncrude Canada Ltd.

Presentation to 8th _{World Congress of Chemical Engineering}

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Acknowledgements

• CONRAD (Canadian Oil sands Network for R&D) support forCONRAD (Canadian Oil sands Network for R&D) support for project, especially for Syncrude Research contributions and feedback throughout the project

• Financial support and collaboration under NRCan programsFinancial support and collaboration under NRCan programs supporting oil sands development, including PERD 1.1.3 Program-Petroleum Conversion for Cleaner Air and ecoETI (Federal government – ecoAction funding)

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Introduction

• Aspects of predicting processability from key marker

components of oil sands ores is needed in order to assess appropriate operating conditions for commercial extraction of bitumen

• Potential contributions from minerology of inorganic fractions, chemistry of bitumen and then the interfaces and surface

property effects between these property effects between these

• Research was conducted to fractionate various samples to determine if correlation between fractions and processability • Question to be addressed: “Does bitumen composition

influence and therefore correlate with bitumen recovery in water extraction processes?”

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Objective

• Various lab techniques were used separate oil sand into bitumen and bitumen free solids, although this is not easily , g y achieved in commercial operations

• Bitumen was then fractionated from corresponding oil sands samples using high performance liquid

sands samples using high performance liquid

chromatography (HPLC) and then carry out further analyses on bitumen fractions as well as overall composition of original oil sands samples

composition of original oil sands samples.

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Oil Sands Samples

• Four oilsands from a previous bitumen recovery study were selected (Energy & Fuels 2008 22 3174 3193)

selected (Energy & Fuels 2008, 22, 3174–3193).

Sample ID Component (% of Oilsands) Bitumen

Recovery %

Bitumen Fines Clay

E7 14.6 4.9 1.6 93.3

E3 9.8 29.9 3.8 91.5

M13 9 9 25 8 6 3 31 7

• Estuarine (E7) processed with high recovery with a high bitumen

M13 9.9 25.8 6.3 31.7

M18 7.9 41.8 5.2 57.5

content and low fines and clay content

• Estuarine (E3) and marine (M13) oil sands have similar

bitumen and fines (<44μm) contents, but high and low bitumen reco eries respecti el

recoveries respectively.

• Marine (M18) oilsand has a very high fines content but intermediate bitumen recovery.

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Characterization Approach

E t

t d bit

t d i t

h lt

• Extracted bitumen was separated into asphaltenes

(asp) and maltenes.

• Application of HPLC to maltenes yields saturates (sat)

aromatics (ar) and resins fractions.

• The resin component is divided into three fractions (R1,

R2 and R3) based on increasing polarity (Fuel

2004, 83,

R2 and R3) based on increasing polarity (Fuel

2004, 83,

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Characterization Approach

Sample

Asphaltenes

Solvent extraction & asphaltene

Sample

Asphaltenes

Maltenes

asphaltene precipitation

Maltenes

HPLC

Aromatics

Saturates

Resins

R1

R2

R3

HPLC

R1

R2

R3

Increasing polarity

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Characterization Methods

Molecular weights:

GPC

Elemental analysis:

C,H,N,S with LECO analyzer

Nitrogen and sulfur types:

X-ray photo electron spectroscopy

Carbon and proton types:

13

_{C NMR,}

1

_{H NMR}

Average structural parameters:

Calculated based on elemental analysis, MW and NMR

results

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Results from SARA analysis

Samples E3, E7, M13 and M18 compare in composition Samples E3, E7, M13 and M18 compare in composition to typical coker feed bitumen (CFB).

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Molecular weights for coker feed bitumen fractions compared to other samples

Molecular weights similar for all samples except slightly Molecular weights similar for all samples except slightly higher for resins in M18.

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Nitrogen and sulfur contents for fractions of samples

• Nitrogen and sulfur content is similar for corresponding fractions of each sample and similar to CFB content.

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Nitrogen and sulfur contents for R1, R2 and R3 fractions

• Nitrogen content increases in increasing HPLC column polarity for separating R1, R2 and R3 fractions

• Nitrogen content in R3 approaches levels measured for asphaltene fraction

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Average structural parameters

(Fuel 1982, 61, 402-410)

Calculations based on molecular weights elemental analysis

Symbol Parameter

Calculations based on molecular weights, elemental analysis,

13_{C NMR and}1_{H NMR.}

Symbol Parameter

C _ar n _{Number of aromatic carbon atoms in average single molecule}

C _alfa n _{Number of alkyl substituents on aromatic ring system in an average}

alfa y g y g

single molecule

C _c n _{Number of carbon atoms at condensed points in aromatic ring in an} average single molecule

K Degree of condensation of aromatic ring system (C _c n _{/ C}

ar n )

L Average paraffinic straight chains. Estimated from the ratios of the

13_{C NMR resonances at 29 7ppm and 14 2ppm} 13_{C NMR resonances at 29.7ppm and 14.2ppm.}

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Average structural parameters

(Fuel 1982, 61, 402-410)

• Sample and fractionsSample and fractions derived from them are similar in composition

c

Sample ID Component (% of Oilsands) Bitumen Recovery % Bitumen Fines Clay

E7 14.6 4.9 1.6 93.3

E3 9 8 29 9 3 8 91 5

E3 9.8 29.9 3.8 91.5

M13 9.9 25.8 6.3 31.7

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Conclusions

• Bulk properties of each extracted bitumen sample andBulk properties of each extracted bitumen sample and corresponding SARA fractions were similar

• C_arn _{, C}

alphan and other structural parameters determined

from NMR results in conjunction with MW and elemental from NMR results in conjunction with MW and elemental analyses show little difference between the samples

• Correlation of sample properties reported here did not

• Correlation of sample properties reported here did not correlate with observed bitumen yield… another factor must be effecting recovery rates

• Other factors therefore must be contributing (for example, surface properties of solids, mineralogy of solids and particle size distribution)

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Questions

Thank-you …. Questions?

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XPS results for nitrogen and sulfur types

for selected fractions from bitumen and

methanol extracts (ME)

• While pyrrole was always the primary nitrogen species, pyridine groups were also present in each case; the

pyridine groups were also present in each case; the

greatest contributions from pyridine species occurred in the ME samples.

• In every case the sulphur species were predominantly thiophenic with some contribution from sulphides.

• The sulphoxide and sulphone species occurred in only p p p y some of the asphaltene fractions from the parent

bitumens; the highest concentrations of this species were found in the ME samples.

found in the ME samples.

• Concurrently with this observation the thiophenic sulfur contents in the methanol extracts are lower than those for the corresponding fractions from bitumen

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Fraction of carbon associated with oxygen for bitumen fractions &

methanol extracts (ME) from C13 _NMR

E3 M18 M13

f ti t d f th i t ti f th

0.08

0.12 f_o estimated from the integration of the

following 13_{C NMR regions (ppm)}

50-70 Aliphatic C-OH, C-OR

145 160 Aromatic C OH C OR

0.04

145-160 Aromatic C-OH, C-OR

160-190 COOH, COOR, acid, ester

R3 Asp ME

0.00

ME has a higher amount of carbon associated with oxygen compared to R3 and asphaltenes.

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Atomic H/C ratios and 13_{C aromaticities}

for bitumen fractions and methanol extracts (ME) extracts (ME) E3 M13 1.6 2 M13 M18 40 50 % 0.8 1.2 H /C 10 20 30 A ro m a ti c it y , % Sat Ar R1 R2 R3 asp ME 0 0.4 Sat Ar R1 R2 R3 asp ME 0 10 A

Differences are small when comparing H/C atomic ratios and aromaticities between ME and resins.

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Average structural parameters for bitumen fractions & methanol

extracts (ME) extracts (ME) E3 M13 M18 60 80 a r 12 16 20 lf a t R1 R2 R3 A ME 0 20 40 C n a t R1 R2 R3 A ME 0 4 8 C n a l

sat ar R1 R2 R3 Asp ME sat ar R1 R2 R3 Asp ME

0.4 0.6 4 6 0 0.2 K R1 R2 R3 A ME 0 2 4 L

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Conclusions

• Molecular weights for methanol extracts from bitumen free oilsands solids are close to those for resin fractions, and , much lower than those for asphaltenes.

• Only minor differences exist between H/C atomic ratios, aromaticities for ME and resins

aromaticities for ME and resins.

• Number of aromatic carbon atoms in molecule; number and chain lengths of alkyl substituents on aromatic rings were

t i ti t i il iti b t th

among parameters pointing to similarities between the methanol extract and resins.

• Degree of condensation of aromatic ring systems for the ME samples are much lower than the values for the

corresponding resin fraction.

• Both elemental sulfur content and the contribution ofBoth elemental sulfur content and the contribution of

thiophenic sulfur in the methanol extract samples is lower than those in the bitumen components.

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Conclusions

• The contributions of elemental nitrogen and carbon

associated with oxygen for the methanol extract are higher

th th f th i d th h lt

than those for the resin and the asphaltenes.

• Owing to its polar nature TIOM may be responsible for increased interaction with bulk bitumen leading to g

associated difficulties with oil release during conventional water based separation processes.

• In all cases the nitrogen species are predominantly pyrrolicIn all cases the nitrogen species are predominantly pyrrolic. Pyrolle rich organic matter is known to undergo oxidative polymerization to form the adhesive material with high a propensity to fouling